The name Napoleon is derived from the Old Italian name Napoleone, which itself comes from the ancient Greek name Νεαπόλιων (Neapolion). This Greek name is a compound of the elements "nea" meaning "new" and "polis" meaning "city". The name essentially translates to "new city" or "from the new city".

One of the earliest recorded instances of this name is Napoleone Orsini, an Italian Roman Catholic prelate who served as Archbishop of Manfredonia from 1328 to 1347. Another early bearer was Napoleone Petrucci, an Italian condottiero and lord of Siena in the late 15th century.

The name gained widespread recognition and fame through Napoleon Bonaparte (1769-1821), the French military leader who rose to prominence during the French Revolution and eventually crowned himself as Emperor of France in 1804. His military conquests and political reforms had a significant impact on the course of European history.

Other notable individuals named Napoleon throughout history include Napoleon III (1808-1873), the nephew of Napoleon Bonaparte who ruled as Emperor of the Second French Empire from 1852 to 1870. Napoleon Sorice (1805-1854) was an Italian poet and playwright, while Napoleon Lapathèque (1824-1892) was a French painter and illustrator.

In the 20th century, Napoleon Hill (1883-1970) was an American self-help author best known for his book "Think and Grow Rich". Napoleon Whiting (1916-1942) was an American naval officer who received the Medal of Honor for his actions during the Battle of Savo Island in World War II.